US3639643A - Method for elimination of the 32 c. phase transition in granules and prills containing free ammonium nitrate and products produced thereby - Google Patents
Method for elimination of the 32 c. phase transition in granules and prills containing free ammonium nitrate and products produced thereby Download PDFInfo
- Publication number
- US3639643A US3639643A US802210A US3639643DA US3639643A US 3639643 A US3639643 A US 3639643A US 802210 A US802210 A US 802210A US 3639643D A US3639643D A US 3639643DA US 3639643 A US3639643 A US 3639643A
- Authority
- US
- United States
- Prior art keywords
- granules
- ammonium nitrate
- nitrate
- prills
- elimination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000008187 granular material Substances 0.000 title abstract description 27
- 238000000034 method Methods 0.000 title abstract description 18
- 230000007704 transition Effects 0.000 title abstract description 8
- 230000008030 elimination Effects 0.000 title abstract description 5
- 238000003379 elimination reaction Methods 0.000 title abstract description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 title description 29
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 19
- 229910002651 NO3 Inorganic materials 0.000 abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 9
- 239000003337 fertilizer Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005422 blasting Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 235000014413 iron hydroxide Nutrition 0.000 description 4
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 235000012054 meals Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012106 screening analysis Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- KKEOZWYTZSNYLJ-UHFFFAOYSA-O triazanium;nitrate;sulfate Chemical compound [NH4+].[NH4+].[NH4+].[O-][N+]([O-])=O.[O-]S([O-])(=O)=O KKEOZWYTZSNYLJ-UHFFFAOYSA-O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C1/00—Ammonium nitrate fertilisers
- C05C1/02—Granulation; Pelletisation; Stabilisation; Colouring
Definitions
- Granular products containing ammonium nitrate are widely used in fertilizers and blasting composition. They are manufactured by prilling and by various granulation methods. In order to avoid caking during storage it is known that the granules can be coatedwith finely dispersed inorganic substances such as kieselguhr.
- the colloidal substance can be silicon hydrate, iron hydroxide or aluminum hydroxide or mixtures of the same which is insoluble in the ammonium nitrate containing melt or solution and which has been precipitated 7' sition causes granules of ammonium nitrate, prepared by" ice therein according to known methods for the manufacture of colloids.
- the invention is based on the surprising discovery that the colloidal hydrates or hydroxides of silica, iron or aluminum effect the phase transitions in the nitrate containing crystals.
- the so called 32-tranmeans of heretofore known methods to disintegrate to a powdery flour after a few temperature cycles around said temperature.
- the granules provided with an internal filler consisting of said hydrates or hydroxides according to this invention can Without changes, be subjected to such a treatment. This is of great practical importance particularly when the ammonium nitrate is manufactured in a country having a tropical climate, or is sold to a purchaser in a country having a tropical climate.
- a prior art solution for eliminating said phase transition and thus eliminating its effect on the strength of the granules is to transform the ammonium nitrate completely into double salts such as ammonium sulfate nitrate. This presupposes however that the other component is included in a stoichiometrical quantity and therefore is an essential part of the final product.
- the colloidal fillers introduced into ammonium nitrate in accordance with this invention have a considerable effect, even when used in small amounts. This is particularly advantageous when the ammonium nitrate or the ammonium nitrate containing product is to be used in blasting compositions, since a high content of inert additives would have a desensitizing influence and could render the product unsuitable for its actual purpose.
- the content of filler can be within the range of 0.12%, and preferably O.2-1%.
- other known blasting components can be included.
- fillers according to this invention can also be used in combination with heretofore known and conventional fillers.
- Millimeters Percent 2 0 1.5-2 2 1.0l.5 69 0.5-1.0 27 0.5 2
- test specimens were crushed after only 5 temperature cycles so that 100% passed through the screen.
- Ammonium nitrate containing an internal filler in accordance with our invention was produced according to the same prilling process as in Example 1.1 and 1.2 but colloidal aluminum hydroxide was precipitated in situ in the nitrate solution. This was carried out by dissolving an aluminum sulfate in the 96% nitrate solution which thereby became somewhat turbid from the partial hydrolysis of the aluminum salt, which also caused a decrease in pH to within the range of 1-2. Immediately before the solution was pumped to the nozzle for prilling it was neutralized with ammonia and under suificient agitation that a homogenous dispersion of colloidal aluminum hydroxide was formed.
- the prills obtained had the same screening analysis and about the same porosity as in Example 1.1. However, the shaking test after repeated temperature cycles showed considerably improved figures, as indicated below:
- Granulation was performed in a screw type granulator with addition of recycled material, whereby granules having essentially a diameter of 48 mm. were obtained. After drying, oversize and undersize granules were screened off, crushed and recycled to the granulation step.
- these coarser prills are particularly advantageous when fertilizing forests.
- the coarser prills are distributed more sparsely and thus the undesired fertilizing of the ground vegetation is reduced while a greater part of the nitrogen penetrates down to the roots of the trees.
- the coarser prills have additional advantage because due to their heavier impact they do not get caught in the tree tops and thus they do not cause so called burns on the foliage and needles of the trees.
- a prerequisite for achieving the mentioned advantages however is that the prills be resistant to the hard impact against the top of the trees and the ground. This means that the prills must not have been weakened by phase transitions.
- Forest fertilizers usually are distributed in winter and are stored in the forest for spreading during the season for this activity, usually the beginning of summer. Temperature shifts have caused the large nitrate granules produced according to heretofore known methods to lose their strength and to sometimes even deteriorate into flour.
- the present invention has resulted in a method for the production of granules which have greater re- Shaking test (percent thru screen)
- EXAMPLE 3 (Relating to large diameter granules of ammonium nitrate) A 94% aqueous solution of ammonium nitrate was admixed with aluminum sulfate and then with ammonia so that it contained 0.5% colloidal Al(OH) based on sistance to shock and temperature change, which results in excellent granules for forest fertilization.
- EXAMPLE 4 (Relating to lime ammonium nitrate) Lime ammonium nitrate containing 26% -N is produced by granulating or prilling of a hot concentrated ammonium nitrate solution containing finely ground limestone flour (meal), and the product obtained is cooled before storage.
- colloidal filler If 1-10% of the quantity of limestone meal is replaced by a colloidal filler the storage properties are improved, which is of particular importance when storing in bulk or high bag piles.
- the colloidal filler is one of the aforementioned oxide hydrates an added economy can be achieved in that the granules do not have to be cooled as much before they leave the production process and can therefore leave with a higher temperature.
- Using these fillers thus results in an important economic advantage in that (a) the cooling drums in existing plants can be operated at higher temperatures, which mean higher capacities and (b) when building new plants smaller and therefore less costly cooling drums can be installed.
- a method for elimination of the 32 C. phase transition in granules and prills containing free ammonium nitrate which comprises precipitating between about 0.1 and 10% of at least one colloidal material selected from the group consisting of silicon hydrates, iron hydroxides, aluminum hydroxides, and mixtures thereof, into a fluid medium containing ammonium nitrate, while the nitrate is still in a fluid condition, said ammonium nitrate being present in said fluid medium in an amount suflicient to provide, upon solidifying free ammonium nitrate which is not in the form of a double salt, and then converting the nitrate in fluid form into a solidified nitrate containing said hydroxides or oxide hydrates substantially uniformly distributed throughout the matrix of the solidified nitrate, which contains said free ammonium nitrate.
- colloidal material is present in an amount between about .01 and 2.0%.
- a granular product containing free ammonium nitrate and between 0.1 and 10% of a colloidal material References Cited UNITED STATES PATENTS 3,282,674 11/1966 Mohr et a1. 71-59 X 3,388,014 6/1968 Russo 14946 X 3,428,418 2/1969 McFarlin et a1 23103 JOHN T. GOOLKASIAN, Primary Examiner J. C. GIL, Assistant Examiner US. Cl. X.R.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE245568 | 1968-02-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3639643A true US3639643A (en) | 1972-02-01 |
Family
ID=20259984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US802210A Expired - Lifetime US3639643A (en) | 1968-02-26 | 1969-02-25 | Method for elimination of the 32 c. phase transition in granules and prills containing free ammonium nitrate and products produced thereby |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3639643A (enrdf_load_html_response) |
| DE (1) | DE1909426A1 (enrdf_load_html_response) |
| FI (1) | FI54094C (enrdf_load_html_response) |
| FR (1) | FR2002594A1 (enrdf_load_html_response) |
| NO (1) | NO123606B (enrdf_load_html_response) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1981001704A1 (en) * | 1979-12-12 | 1981-06-25 | Nitram Inc | Ammonium nitrate process and products |
| US4408998A (en) * | 1981-06-19 | 1983-10-11 | Unie Van Kunstmestfabrieken Bv | Process for preparing thermally stable ammonium nitrate- containing granules |
| WO2001049608A1 (en) * | 2000-01-04 | 2001-07-12 | Kemira Agro Oy | Process for stabilizing ammonium nitrate |
| US6726788B2 (en) | 1994-01-19 | 2004-04-27 | Universal Propulsion Company, Inc. | Preparation of strengthened ammonium nitrate propellants |
| US20220098127A1 (en) * | 2020-07-31 | 2022-03-31 | Dyno Nobel Asia Pacific Pty Limited | Phase-stabilized ammonium nitrate explosives |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4268490A (en) * | 1978-07-03 | 1981-05-19 | Ici Australia Limited | Processes of making prilled ammonium nitrate compositions |
| ATA443881A (de) * | 1981-10-15 | 1983-02-15 | Sanvita Dipl Ing Franz Cervink | Verfahren zur herstellung eines stickstoffduengers |
-
1969
- 1969-02-19 FI FI522/69A patent/FI54094C/fi active
- 1969-02-20 NO NO0702/69A patent/NO123606B/no unknown
- 1969-02-21 FR FR6904508A patent/FR2002594A1/fr active Pending
- 1969-02-25 US US802210A patent/US3639643A/en not_active Expired - Lifetime
- 1969-02-25 DE DE19691909426 patent/DE1909426A1/de active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1981001704A1 (en) * | 1979-12-12 | 1981-06-25 | Nitram Inc | Ammonium nitrate process and products |
| US4408998A (en) * | 1981-06-19 | 1983-10-11 | Unie Van Kunstmestfabrieken Bv | Process for preparing thermally stable ammonium nitrate- containing granules |
| US6726788B2 (en) | 1994-01-19 | 2004-04-27 | Universal Propulsion Company, Inc. | Preparation of strengthened ammonium nitrate propellants |
| US20050092406A1 (en) * | 1994-01-19 | 2005-05-05 | Fleming Wayne C. | Ammonium nitrate propellants and methods for preparing the same |
| US6913661B2 (en) | 1994-01-19 | 2005-07-05 | Universal Propulsion Company, Inc. | Ammonium nitrate propellants and methods for preparing the same |
| WO2001049608A1 (en) * | 2000-01-04 | 2001-07-12 | Kemira Agro Oy | Process for stabilizing ammonium nitrate |
| US20030099589A1 (en) * | 2000-01-04 | 2003-05-29 | Heikki Hero | Proces for stabilizing ammonium nitrate |
| US20050276740A1 (en) * | 2000-01-04 | 2005-12-15 | Heikki Hero | Process for stabilizing ammonium nitrate |
| US7014828B2 (en) | 2000-01-04 | 2006-03-21 | Kemira Growhow Oyj | Process for stabilizing ammonium nitrate |
| US7147830B2 (en) | 2000-01-04 | 2006-12-12 | Kemira Growhow Oyj | Stabilized ammonium nitrate granules |
| KR100722962B1 (ko) | 2000-01-04 | 2007-05-30 | 케미라 그로하우 오와이제이 | 안정한 질산 암모늄의 제조 방법 |
| US20220098127A1 (en) * | 2020-07-31 | 2022-03-31 | Dyno Nobel Asia Pacific Pty Limited | Phase-stabilized ammonium nitrate explosives |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2002594A1 (enrdf_load_html_response) | 1969-10-31 |
| FI54094C (fi) | 1978-10-10 |
| DE1909426A1 (de) | 1969-09-11 |
| NO123606B (enrdf_load_html_response) | 1971-12-20 |
| FI54094B (fi) | 1978-06-30 |
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